Parkin Gerard
Department of Chemistry, Columbia University, New York, New York 10027, USA.
New J Chem. 2007;31(12):1996-2014. doi: 10.1039/b712012e.
The tripodal tris(2-mercapto-1-R-imidazolyl)hydroborato ligand system, [Tm(R)], and its selenium counterpart, [Tse(R)], provide useful platforms for investigating organometallic and bioinorganic aspects of the chemistry of zinc, cadmium and mercury in sulfur-rich and selenium-rich coordination environments. For example, the tridentate [Tm(R)] ligand provides an [S(3)] donor array that is of use for mimicking aspects of zinc enzymes and proteins that have sulfur-rich active sites, such as the Ada DNA repair protein. With respect to mercury, an interesting application of the [Tm(Bu(t) )] ligand is the synthesis of the mercury alkyl compounds [Tm(Bu(t) )]HgR (R = Me, Et) that react with PhSH to yield [Tm(Bu(t) )]HgSPh and RH, a reaction that emulates mercury detoxification by the organomercurial lyase, MerB. In addition to the tridentate [Tm(R)] and [Tse(R)] ligands, applications of the bidentate counterparts, [Bm(R)] and [Bse(R)] are also described.
三脚架型三(2-巯基-1-R-咪唑基)硼氢配体体系[Tm(R)]及其硒类似物[Tse(R)],为研究锌、镉和汞在富硫和富硒配位环境中的有机金属化学和生物无机化学方面提供了有用的平台。例如,三齿配体[Tm(R)]提供了一个[S(3)]供体阵列,可用于模拟具有富硫活性位点的锌酶和蛋白质的某些方面,如Ada DNA修复蛋白。关于汞,[Tm(Bu(t) )]配体的一个有趣应用是合成汞烷基化合物[Tm(Bu(t) )]HgR(R = 甲基、乙基),它们与PhSH反应生成[Tm(Bu(t) )]HgSPh和RH,该反应模拟了有机汞裂解酶MerB对汞的解毒作用。除了三齿配体[Tm(R)]和[Tse(R)]外,还描述了双齿类似物[Bm(R)]和[Bse(R)]的应用。